Substituted dihydroxy-diphenyls



Patented June 9, 1942 I "i UNITED STATES PATENT OFFICE SUBSTITUTED DIHYD'ROXY-DIPHENYLS Edgar O. Britton and John E. Livak, Midland,

Mich., assignors to The Dow Chemical Company, Midland, Mich., a corporation of Michigan No Drawing. Original application June 23, 1939,

Serial No. 280,846. Divided and this application May 2, 1941, Serial No. 391,510

2 Claims. (Cl; 260-620) This invention relates to certain new deriva- The reactions involved in such mode of procedure tives of 4.4'-dihydroxy-diphenyl and in particumaybe represented as follows: lar concerns substituted dihydroxy-diphenyls OH having the general formula I wherein R represents an alkyl group containing at least 4 carbon atoms, a cycloalkyl group, or an aralkyl group. Examples of such compounds are /CvHw 3.3-di-n-butyl-4.4'-dihydroxy-dipheny1, 3.3-di- 2 Cu H1 isobutyl-4.4'-dihydroxy-diphenyl, 3.3-di-tertia -OO- ryamy1-4.4'-dihydroxy-dipheny1, 3.3'-di-n-octyl- 4.4'dihydroxy-diphenyl, 3.3 di-benzyl-4.4-dihydroxy diphenyl, 3.3-di-cycloheXyl-4.4-dihydroxy-diphenyl, etc. lia /CtHn The substituted dihydroxy-diphenyls having the above general formula are usually obtained -O in the form of white crystalline solids which are substantially insoluble in water but are soluble in Wherem R represents a lower alkyl b- All common organic solvents e. acetone, petrole of these reactions are of a well-known type and um ether, carbon tetrachloride, benzene, etc. e most Suitable condition? f01 efieeting them They are useful as intermediates in the prepara- 2 W111 be aJPDaTeIlb t0 ffihese l ed n t ar tion of dyes and dye intermediates, plasticizers, alkyl 'Substltuted dlhydmxydlpbenyls Wetting agents, pharmaceuticals, toxicants, etc. may also be Prepared by the h d ehatlon of The alkyland cycloalkyl-substituted dih the Corresponding alkenyl-subsiututed dlhydroxyd oxy djph nyl of the present class may be dlphenyls, certain of which compounds are depared by forming t paraqodo derivative f the scrlbed and claimed in our U. S. Patent No. corresponding ortho-alkyl or cycloalkyl phenol $229,010 Issue? January f 1 41. Thus, 3.3 -d1- and thereafter condensing two molecules of such 'Q l h may e p iodo derivative to form the desired dihydroxy-did; y hydrogenating 3.3'-d1 -(2-methylallyl) phenyl compound. Since the free hydroxyl yd Xyd1phenyl, 3.3'-d1-n -hexy1-4.4 '-d1- group of the phenol is reactive under the condi- 5 hydroXy-dlphehyl y y g g '-d I tions employed for these reactions, it is necessary propylallyl) -4-4'(51111?dr cfxy-dlphenyl, The t protect t hydroxyl group fo example by hydrogenation reactlon is preferably carried out I etherification, during the iodination and condenby the direct addition of gaseous hydrogen nder sation reactions and thereafter regenerate the pFessllre 0 81 5011mm} f the a nyllhydroxyfree phenol. For example, in preparing 3.3'-d 40 dlphenyl compound 1n an 1nert solvent in the hexyl-4.4dihydroxy-diphenyl, oheXy1phenol is presence of a hydrogenat on atalyse such as first reacted with an alkylating agent, e. g. dinickel, pl tl u px c. e re ct n takes methyl sulphate, ethyl chloride, etc., in the place quit re ly at o l y mp r known manner to form an o-hexyl-phenyl ether, g. 20-30 0., f deSlTed, el: p atu e. g. o-hexyl-anisole, o-hexyl-phenetole, etc., may be p ye pon com l of the rewhich compound is then reacted with iodine in action, the catalyst is filtered oif and the hydrothe presence of mercuric oxide or other strong gene/Bed Product recovered e v from e oxidizing agent to form the correspondin paction mixture and purified by crystallization iodo-o-hexyl-phenyl ether. To molecules of this Om a su able Solvent. latter compound are then condensed, employing he a y -di ydroxyd phenyls of the prescopper powder or other suitable condensing ent class ay be prepared by the condensation agent, to form a di-ether of 3.3'-di-hexyl-4.4- of a p-iodo-o-aralkyl-phenyl ether, as hereindihydroxy-diphenyl from which product the debefore described, although they are more consired 3.3-di-hexyl-4.4-dihydroxy-dipheny1 may veniently prepared by the direct aralkylation of be obtained by treatment with hydrogen iodide. 4.4'-dihydroxy-diphenyl. In carrying out such reaction, the 4.4-dihydroxy-dipheny1 is first reacted with an alkali to form an alkali-metal salt thereof and the latter compound is heated with an aralkyl halide, e. g. benzyl bromide, alphachloroethyl benzene, etc., at reflux temperature until the reaction is complete. In the absence of excess alkali, the desired product is formed directly and is recovered from the reaction mix-' 256 grams of iodine was added in 30 gram portions over a period of 20 minutes to a mixture of 190 grams of o-cyclohexyl-anisole (prepared by the methylation of o-cyclohexyl-phenol), 108 grams of mercuric oxide, and 550 grams of ethyl alcohol maintained at a temperature of about 25-55 C. The mixture was then heated at reflux temperature for 4 hours after which time it was cooled and filtered, and the alcohol was removed by distillation. The distillation residue was washed with a dilute aqueous sodium bisulfite solution to destroy unreacted iodine, and the washed product was extracted with carbon tetrachloride. The carbon tetrachloride extract was then iractionally distilled whereby there was obtained p-iodo-o-cyclohexyl-=anisole, an oily liquid distilling at approximately 165l75 C. under 5 millimeters pressure. A mixture of 110 grams of this product and '75 grams of copper powder was heated at a temperature of about 260-300 C. for /2 hour after which time the mixture was cooled and extracted with benzene. The benzene was evaporated from the extract and the crystalline residue was recrystallized from glacial acetic acid whereby 3.3-di-cyclohexyl-4.4-di-methoxy-diphenyl was obtained in the form of glistening white plates melting at 1'74.5175.5 C. 28.4 grams of the 3.3-di-cyclohexyl-4.4'-di-methoxy-dipheny1 thus obtained was then dissolved in approximately 100 grams of phenol by warming to 120 C., and 72.7 grams of hydrogen iodide in the form of a 57 per .cent aqueous solution was added gradually with stirring. The mixture was then heated at reflux temperature (125 C.) for 2 hours after which time it was cooled and poured into 500 cc. of water, whereby the 3.3-di-cyclohexyl-4.4-dihydroxy-diphenyl product was precipitated as a white crystalline solid. After recrystallization from glacial acetic acid, this compound had a melting point of 209-213 C.

Example 2 11.3 grams of 3-.3-di-(2-methylallyl) -4.4-dihydroxy-diphenyl (M. P.=9'l-97.5 C.) prepared by the rearrangement of 4.4'-di- (2-methy1- allyloxy) -diphenyl, was dissolved in 60 grams of ethyl alcohol, and, after the addition of 0.1 gram of platinum oxide, was treated with gaseous hydrogen under pressure in a Burgess-Parr hydrogenation apparatus. The theoretical amount of hydrogen (0.08 mole) was absorbed in about 3 minutes. Upon conclusion of the hydrogenation, the alcohol solution was filtered to remove the platinum oxide catalyst and the filtrate was evaporated to dryness on a steam bath. The

residue was recrystallized twice from a benzenepetroleum ether mixture whereby 3.3'-di-isobutyl-4.4-dihydroxy-diphenyl was obtained in the form of a white crystalline solid melting at 136- Example 3 A suspension of 53.2 grams of the di-sodium salt of 4.4'-dihydroXy-dipheny1 in 345 grams of toluene was heated to reflux temperature to drive ofiwater of crystallization after which time 50.6 grams of benzyl .chloride was added gradually with stirring at a temperature of about 25 C. The mixture was then heated at reflux temperature (112 C.) for 8 hours, cooled, washed with petroleum ether and water, and filtered. The precipitate, consisting of crude 3.3-dibenzyl-4.4-dihydroxy-diphenyl, was digested with dilute aqueous sodium hydroxide, filtered, and the alkaline filtrate was acidified with dilute aqueous hydrochloric acid; whereby the 3.3- dibenzyl-4.4-dihydroxy-diphenyl product was precipitated as a white crystalline solid. After two recrystallizations from benzene, the compound had a melting point of approximately 151-158 C.

Other substituted dihydroxy-diphenyl compounds of the present class which may be prepared as herein described include 3.3'-di-tertiarybutyl-4.4'-dihydroxy-diphenyl, 3.3'-di-nheptyl- 4.4-dihydroxy-diphenyl, 3.3'-di-isoamyl-4.4'-dihydroxy-diphenyl, 3.3-di-tertiaryoctyl-4.4'-dihydroxy-diphenyl, 3.3 -di-beta-phenylethyl-4.4 -dihydroxy-diphenyl, 3.3 -di-cyclopentyl-4.4-dihydroxy-diphenyl, 3.3 di gamma phenylpropyl- 4.4 -dihydroxy-diphenyl, 3.3 -di-lauryl-4.4 -dihydroxy-diphenyl, etc.

This application is a division of our copending application Serial No. 280,846, filed June 23, 1939 now Patent #2,260,739, issued Oct. 28, 1941.

We claim:

1. A substituted dihydroxy-diphenyl compound having the general formula EDGAR C. BRITTON. JOHN E. LIVAK. 

